CN114079045B - Porous silicon/carbon composite material synthesized in situ by taking porous polymer microspheres as templates, preparation method and lithium ion battery - Google Patents
Porous silicon/carbon composite material synthesized in situ by taking porous polymer microspheres as templates, preparation method and lithium ion battery Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 68
- 239000004005 microsphere Substances 0.000 title claims abstract description 67
- 239000002131 composite material Substances 0.000 title claims abstract description 59
- 229910021426 porous silicon Inorganic materials 0.000 title claims abstract description 54
- 229920000642 polymer Polymers 0.000 title claims abstract description 33
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 23
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000013067 intermediate product Substances 0.000 claims abstract description 42
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000010703 silicon Substances 0.000 claims abstract description 33
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000001035 drying Methods 0.000 claims abstract description 24
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000010405 anode material Substances 0.000 claims abstract description 23
- 239000011148 porous material Substances 0.000 claims abstract description 21
- 239000008367 deionised water Substances 0.000 claims abstract description 19
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 19
- 238000005406 washing Methods 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 18
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 17
- 238000001914 filtration Methods 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 238000005554 pickling Methods 0.000 claims abstract description 13
- 239000000725 suspension Substances 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims abstract description 11
- 238000011946 reduction process Methods 0.000 claims abstract description 10
- 238000000227 grinding Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000011259 mixed solution Substances 0.000 claims abstract description 4
- 239000012467 final product Substances 0.000 claims abstract description 3
- 239000002245 particle Substances 0.000 claims description 29
- -1 polyethylene Polymers 0.000 claims description 17
- 239000000843 powder Substances 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- 238000003786 synthesis reaction Methods 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 7
- 239000004698 Polyethylene Substances 0.000 claims description 6
- 239000004793 Polystyrene Substances 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- 229910000103 lithium hydride Inorganic materials 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229920000573 polyethylene Polymers 0.000 claims description 6
- 229920002223 polystyrene Polymers 0.000 claims description 6
- 229920002635 polyurethane Polymers 0.000 claims description 6
- 239000004814 polyurethane Substances 0.000 claims description 6
- 239000004800 polyvinyl chloride Substances 0.000 claims description 6
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 6
- 229910000048 titanium hydride Inorganic materials 0.000 claims description 6
- 239000004743 Polypropylene Substances 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 5
- 229920001155 polypropylene Polymers 0.000 claims description 5
- 239000004115 Sodium Silicate Substances 0.000 claims description 4
- ZZHNUBIHHLQNHX-UHFFFAOYSA-N butoxysilane Chemical compound CCCCO[SiH3] ZZHNUBIHHLQNHX-UHFFFAOYSA-N 0.000 claims description 4
- 239000008151 electrolyte solution Substances 0.000 claims description 4
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- ARYZCSRUUPFYMY-UHFFFAOYSA-N methoxysilane Chemical compound CO[SiH3] ARYZCSRUUPFYMY-UHFFFAOYSA-N 0.000 claims description 4
- ZMYXZXUHYAGGKG-UHFFFAOYSA-N propoxysilane Chemical compound CCCO[SiH3] ZMYXZXUHYAGGKG-UHFFFAOYSA-N 0.000 claims description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 4
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 238000009792 diffusion process Methods 0.000 claims description 2
- 238000009826 distribution Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 238000009736 wetting Methods 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 abstract description 16
- 238000009830 intercalation Methods 0.000 abstract description 7
- 230000002687 intercalation Effects 0.000 abstract description 7
- 230000008859 change Effects 0.000 abstract description 5
- 238000013329 compounding Methods 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 15
- 239000000463 material Substances 0.000 description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 238000011056 performance test Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000007773 negative electrode material Substances 0.000 description 6
- 239000000377 silicon dioxide Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000002210 silicon-based material Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052814 silicon oxide Inorganic materials 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000005543 nano-size silicon particle Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000011863 silicon-based powder Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003090 exacerbative effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000007709 nanocrystallization Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011856 silicon-based particle Substances 0.000 description 1
- 239000002153 silicon-carbon composite material Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005556 structure-activity relationship Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a porous silicon/carbon composite anode material synthesized in situ by taking porous polymer microspheres as templates, a preparation method and a lithium ion battery, wherein the preparation process comprises the following steps: adding porous polymer microspheres into water, heating and stirring to obtain a suspension solution; adding a silicon source into the suspension solution to obtain a mixed solution; filtering, washing with deionized water, drying, adding reducing agent, grinding and mixing to obtain an intermediate product A; treating the intermediate product A through a thermal reduction process to obtain an intermediate product B; and (3) pickling the intermediate product B, and washing, filtering and drying the intermediate product B by deionized water to obtain a final product. Compared with the prior art, the carbon layer obtained by in-situ compounding can better improve the conductivity, the circulation stability, the charge-discharge efficiency, the multiplying power performance and other electrochemical performances of the silicon negative electrode, and the unique micro-nano pore reserves a lithium intercalation expansion space for silicon, so that the absolute volume change of the composite material in the charge-discharge process is reduced.
Description
Technical Field
The invention relates to the field of preparation of lithium ion battery cathode materials, in particular to a porous silicon/carbon composite material synthesized in situ by taking porous polymer microspheres as templates, a preparation method and a lithium ion battery.
Background
With the progress of electronic industry, electric automobile and aerospace technology, higher requirements are put on the performance of lithium ion batteries. Therefore, to realize breakthrough of lithium ion battery in energy density and power density, a critical "bottleneck" problem is how to design and develop new electrode materials. In the research field of lithium ion batteries, the focus of the research is on negative electrode materials. Currently graphite electrodes have a low theoretical lithium storage capacity (lics) 6 372 mAh/g) makes it difficult to make breakthrough progress. Therefore, research and development of a novel negative electrode material with high specific capacity, high charge and discharge efficiency, high cycle performance, high rate charge and discharge performance, high safety and low cost are urgent, and have become a hot topic in the research field of lithium ion batteries and have very important significance for the development of lithium ion batteries.
Silicon-based materials are widely recognized as the most important high capacity negative electrode materials. Besides the advantage of abundant reserves in nature, the theoretical lithium intercalation capacity is 4200mAh/g (Li 22 Si 5 9800 mAh/mL), the lithium intercalation/deintercalation platform is high, and the safety performance is high. Although the silicon cathode material has good application prospect, because the silicon volume is expanded to 420 percent in the charging and discharging process, the particles are easy to be crushed under the action of stress,causing rapid decay in material capacity. In addition, the repeated volume expansion and contraction makes the interface between silicon and electrolyte quite unstable, resulting in the continuous destroyed SEI film on the surface of the negative electrode to grow again, which consumes a great deal of Li in the electrolyte + So that the charge and discharge efficiency is deteriorated, and at the same time, an excessively thick SEI film affects Li + Increases the internal resistance and polarization of the cell, further exacerbating the capacity fade of the material.
In the prior art, in order to improve the cycle performance of the silicon material, the main strategy adopted is to design the composition and microstructure of the material so as to adapt to the volume effect of silicon and maintain the electrode conductive network, and the main approaches include nanocrystallization, compounding, porosification and the like. However, the use of nanomaterials has poor effect on improving the cycle performance of alloy materials; single active doping or inert doping, although being capable of partially inhibiting the volume expansion of silicon-based materials, still cannot completely solve the problems of silicon dispersion and agglomeration; other methods have limited stability enhancing effects and have greater environmental pollution.
Chinese patent CN103165874a discloses a porous silicon negative electrode material for lithium ion battery, and preparation method and use thereof. The method takes silicon-based alloy powder as a raw material and reacts with inorganic acid to generate porous silicon particles; and cleaning the surface of the porous silicon material by using an HF solution to remove the surface silicon oxide, and then washing and drying the porous silicon material. The material has high capacity, but has low initial coulombic efficiency (about 60%), and the HF solution is used in the preparation process, thus causing environmental pollution.
Chinese patent CN102157731a discloses a silicon/carbon composite negative electrode material for lithium ion battery and its preparation method. The method comprises the steps of preparing a porous silicon matrix by adopting magnesia-reduced mesoporous silica, and then coating carbon to obtain the silicon/carbon composite anode material. The mesoporous silica and magnesium powder used by the method have high cost, and are not beneficial to industrial production.
Chinese patent CN102969489a discloses a silicon/carbon composite material and a method for preparing the same. The method is that silicon dioxide is reduced by metal (such as lithium, sodium, potassium, magnesium and the like) with activity larger than that of silicon to obtain silicon and metal oxide, and the silicon/carbon composite material is obtained after acid corrosion and hydrothermal carbon coating. The metals used in the method are all metals with strong activity, and the simple substance has high cost and high danger, so the method is not beneficial to industrial production.
CN103531760 discloses a porous silicon/carbon composite microsphere with yolk-eggshell structure and its preparation method, the microsphere core provided is porous submicron silicon sphere with diameter of 400-900 nm, shell is porous carbon with thickness of 10-60 nm and cavity inner diameter of 800-1400 nm, and its preparation method is that SiO is used 2 Coating the core with carbon source, and sintering to obtain porous carbon coated SiO 2 Treating the powder with alkali to obtain SiO 2 Obtaining porous carbon coated SiO with yolk-eggshell structure 2 Powder, then reducing SiO by magnesian reduction 2 Reducing into silicon powder, and finally treating redundant silicon dioxide through HF to obtain the porous carbon coated porous silicon/carbon composite microsphere with a yolk-eggshell structure.
Disclosure of Invention
In order to solve the problems in the prior art, the invention designs and constructs a more superior porous structure, and provides a porous silicon/carbon composite material synthesized in situ by taking porous polymer microspheres as templates, a preparation method and a lithium ion battery, so that the reversibility and the cycling stability of the charge and discharge process of the porous silicon/carbon anode material are improved.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
the preparation method for in-situ synthesis of the porous silicon/carbon composite anode material by taking the porous polystyrene microspheres as the templates comprises the following steps:
the method for in-situ synthesis of the porous silicon/carbon composite anode material by taking the porous polymer microspheres as templates comprises the following steps:
s1: adding the porous polymer microspheres into water, heating and stirring to uniformly disperse the porous polymer microspheres and obtain a suspension solution;
s2: adding a silicon source into the suspension solution obtained in the step S1, and continuously heating and stirring to obtain a mixed solution;
s3: filtering, washing with deionized water, drying, adding reducing agent, grinding and mixing to obtain an intermediate product A;
s4: treating the intermediate product A through a thermal reduction process to obtain an intermediate product B;
s5: and (3) carrying out acid washing on the intermediate product B obtained in the step (S4), and then washing, filtering and drying by deionized water to obtain the final product porous silicon/carbon composite anode material.
Further, the porous polymer microsphere in S1 is one or a mixture of a plurality of porous polystyrene microsphere, porous polyethylene microsphere, porous polyvinyl chloride microsphere, porous polypropylene microsphere and porous polyurethane microsphere;
the average particle diameter D50 of the porous polymer microsphere is 500 nm-25 mu m, the pore distribution is uniform, and the pore size is 20-200 nm.
In the technical scheme, the average particle size of the porous polymer microspheres and the size of the gaps are critical to the realization of the final performance effect, and the smaller the average particle size of the porous polymer microspheres is, the smaller the corresponding pore size is, however, the too small average particle size (when the D50 is smaller than 500 nm) of the porous polymer microspheres is, the too small pore size (when the D50 is smaller than 20 nm) can lead to difficult industrial production, and the performance optimization of the prepared porous silicon/carbon composite anode material is not facilitated, so that the performance is obviously reduced; when the average particle diameter D50 is too large (more than 25 mu m), the pore size is too large (more than 200 nm), the specific capacity and the first efficiency are obviously reduced, and the capacity retention after multiple cycles is not facilitated, so that the limitation that the average particle diameter D50 of the porous polymer microsphere is 500-25 mu m and the pore size is 20-200 nm is the core parameter limitation of the structure-activity relationship in the system.
Further, the heating temperature in S1 and S2 is 40-60 ℃, the stirring time is 20-40 min, and the stirring speed is 200-2000 r/min.
Further, in S2, the silicon source is one or a mixture of several of ethyl silicate, methyl silicate, sodium silicate, methoxy silane, ethoxy silane, propoxy silane and butoxy silane, the mass ratio of the porous polymer microsphere to the silicon source is 1:1-1:100, and the mass ratio of the porous polymer microsphere to the silicon source is preferably 1:10-1:50.
Further, the drying temperature in S3 is 50-100 ℃ for 1-3 hours.
Further, the reducing agent in S4 is one or a mixture of more of titanium hydride powder, lithium hydride powder and aluminum powder;
the particle size of the reducing agent is 3-20 mu m, the mass ratio of the reducing agent to the silicon source is 5:1-1:5, and the mass ratio of the reducing agent to the silicon source is preferably 3:1-1:3.
Further, the thermal reduction process in S4 is: performing thermal reduction on the intermediate product A in a vacuum or inert protective gas atmosphere;
the temperature of the thermal reduction process is 800-1100 ℃, the temperature rising speed is 2-20 ℃, and the heat preservation time is 1-8 h.
Further, the inert shielding gas is nitrogen or argon.
Further, in S4, any one of a vacuum furnace, a box furnace, a tube furnace, a pusher kiln, a roller kiln and a rotary kiln is adopted for carrying out the thermal reduction process.
Further, hydrochloric acid or sulfuric acid with the concentration of 2.0-7.0 mol/L is adopted as pickling solution in the pickling process in the S5, and the pickling time is 0.5-3 h;
and S5, the drying process is as follows: drying under vacuum or inert gas (nitrogen or argon) at 50-100 deg.c for 1-3 hr.
Compared with the prior art, the invention has the following advantages:
1) The template is one or more of porous polyethylene microspheres, porous polyvinyl chloride microspheres, porous polypropylene microspheres and porous polyurethane microspheres, and the porous silicon/carbon composite material is synthesized in situ by carbonization reaction which synchronously occurs in the thermal reduction process.
2) According to the invention, one or more of porous polyethylene microspheres, porous polyvinyl chloride microspheres, porous polypropylene microspheres and porous polyurethane microspheres are used as templates, and the prepared porous silicon/carbon composite material has a uniform and mutually communicated three-dimensional pore structure, so that the contact area of the porous carbon silicon composite material and an electrolyte solution is increased, the penetration and wetting of the electrolyte solution are facilitated, the diffusion path of lithium ions is shortened, the reactive sites are increased, the electrochemical reaction efficiency is improved, and the ionic conductivity of the material is improved, thereby enhancing the rate capability of the material. On the other hand, the carbon layer formed by in-situ carbonization can inhibit the volume expansion of silicon, and the special porous structure reserves an expansion space for silicon, so that the absolute expansion of the material outwards is reduced, the cycle performance of the material is improved, and the high-rate long-cycle charge and discharge performance of the electrode is improved.
3) The reducing agent is one or more of titanium hydride powder, lithium hydride powder and aluminum powder, has stronger reducing capability, is relatively safe and controllable in the whole reducing process, and is a key technical element for controllably producing the intermediate product B.
By combining the technical advantages, the invention skillfully combines porous polymer microspheres with a silicon source (one or more of ethyl silicate, methyl silicate, sodium silicate, methoxysilane, ethoxysilane, propoxysilane and butoxysilane), realizes advantage complementation by utilizing the synergistic effect of the porous polymer microspheres, effectively inhibits the volume change of the porous silicon/carbon composite material in the lithium intercalation process, and also improves the problem that the micro-nano structure of the existing nano silicon negative electrode material in the market is easy to agglomerate. Furthermore, the in-situ composite carbon layer can better improve the conductivity, the circulation stability, the charge and discharge efficiency, the multiplying power performance and other electrochemical performances of the silicon negative electrode. The unique micro-nano pore reserves a lithium intercalation expansion space for silicon, and reduces the absolute volume change of the composite material in the charge and discharge process. Therefore, the porous silicon/carbon composite material prepared by the method has high conductivity, long-cycle stability and excellent high-rate charge and discharge performance.
The porous polystyrene microsphere is used as a template for in-situ synthesis of the porous silicon/carbon composite anode material, is hopeful to replace graphite to become a novel lithium ion battery anode material, and has high value in the application fields of pure electric vehicles and hybrid electric vehicles.
Drawings
FIG. 1 is a process flow diagram of a porous silicon/carbon composite of the present invention;
FIG. 2 is a schematic structural view of a porous silicon/carbon composite anode material prepared by the invention;
FIG. 3 is a charge-discharge curve of the porous silicon/carbon composite material obtained in example 2 at a current density of 0.1C;
fig. 4 is a graph of the cycling performance and coulombic efficiency of the porous silicon/carbon composite obtained in example 2 at a current density of 0.5C.
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples.
Example 1:
referring to FIG. 1, 50g of porous polystyrene microspheres with the particle size D50 of 500nm and the pore size of about 20nm are taken, added into a proper amount of water, heated to 40 ℃, stirred for 20min at 200r/min, and uniformly dispersed; then 50g of ethyl silicate was slowly added to the resulting suspension and stirring was continued at 200r/min for 20min at 40 ℃; and then filtering, washing with deionized water, drying at 50 ℃ for 1h, adding 250g of aluminum powder with the particle size of 3 mu m as a reducing agent, grinding and mixing to obtain an intermediate product A.
Heating to 800 ℃ at 2 ℃/min, preserving heat for 1h under vacuum atmosphere, and reducing the intermediate product A to obtain an intermediate product B. The intermediate product B is put into 2.0mol/L hydrochloric acid for pickling for 0.5h, and is washed by deionized water, filtered, and heat-preserved for 1h at 50 ℃ for drying to obtain the porous silicon/carbon composite material, see figure 2.
The electrochemical performance test is carried out on the half cell composed of the porous silicon/carbon composite material and metallic lithium, and the test multiplying power is 0.1C (first) +0.5C (cycle), and the charge-discharge voltage is 0.005-2.0V, as shown in figure 3. The specific discharge capacity of the negative electrode plate can reach 2195.0mAh/g, the first efficiency is 88.3%, and the capacity of 92.2% can be maintained after 100 cycles.
Example 2:
taking 50g of porous polyvinyl chloride microspheres with the particle size D50 of 5 mu m and the pore size of about 70nm, adding the porous polyvinyl chloride microspheres into a proper amount of water, heating to 50 ℃, stirring for 30min at 500r/min, and uniformly dispersing the microspheres; 600g of methyl silicate and 400g of sodium silicate are then slowly added to the suspension obtained and stirring is continued at 500r/min for 40min at 50 ℃; and filtering, washing with deionized water, drying at 70 ℃ for 2 hours, adding 3000g of aluminum powder with the particle size of 5 mu m as a reducing agent, grinding and mixing to obtain an intermediate product A.
Heating to 900 ℃ at 5 ℃/min, preserving heat for 2 hours under argon atmosphere, and reducing the intermediate product A to obtain an intermediate product B. And (3) placing the intermediate product B into sulfuric acid with the concentration of 3.0mol/L for pickling for 1h, washing with deionized water, filtering, and carrying out heat preservation at 80 ℃ for 2h and drying to obtain the porous silicon/carbon composite material.
The electrochemical performance test is carried out on the half cell composed of the porous silicon/carbon composite material and metallic lithium, and the test multiplying power is 0.1C (first) +0.5C (cycle), and the charge-discharge voltage is 0.005-2.0V, as shown in figure 4. The specific discharge capacity of the negative electrode plate can reach 2109.8mAh/g, the first efficiency is 92.3%, and the capacity of 93.3% can be still maintained after 100 cycles.
Example 3:
taking 20g of porous polyethylene microspheres with the particle size D50 of 15 mu m and the pore size of about 90nm and 30g of porous polyurethane microspheres with the particle size D50 of 15 mu m and the pore size of about 70nm, adding a proper amount of water, heating to 55 ℃, and stirring for 35min at 600 r/mm to uniformly disperse the microspheres; then, 700g of methoxysilane and 800g of ethoxysilane were slowly added to the resulting suspension, and stirring was continued at 55℃for 40min at 600 r/min; and then filtering, washing with deionized water, drying at 80 ℃ for 1.5 hours, adding 650g of aluminum powder with the particle size of 8 mu m and 850g of titanium hydride powder with the particle size of 10 mu m which are uniformly mixed as reducing agents, and grinding and mixing to obtain an intermediate product A.
Heating to 950 ℃ at 10 ℃/min, preserving heat for 4 hours under nitrogen atmosphere, and reducing the intermediate product A to obtain an intermediate product B. And (3) placing the intermediate product B into sulfuric acid with the concentration of 3.0mol/L for pickling for 2 hours, washing with deionized water, filtering, and carrying out heat preservation at the temperature of 90 ℃ for 2 hours and drying to obtain the porous silicon/carbon composite material.
And (3) performing electrochemical performance test on the half battery formed by the porous silicon/carbon composite material and the metallic lithium, wherein the test multiplying power is 0.1C (first time) +0.5C (circulation), and the charge-discharge voltage is 0.005-2.0V. The specific discharge capacity of the negative electrode plate can reach 2180.5mAh/g, the first efficiency is 89.3%, and the capacity of 91.5% can be maintained after 100 cycles.
Example 4:
10g of porous polyethylene microspheres with the particle size D50 of 15 mu m and the pore size of about 90nm and 40g of porous polypropylene microspheres with the particle size D50 of 20 mu m and the pore size of about 100nm are taken, added into a proper amount of water, heated to 55 ℃, stirred for 35min at 800r/min, and uniformly dispersed; subsequently, 1000g of propoxysilane and 1000g of butoxysilane were slowly added to the resulting suspension and stirring was continued at 55℃for 30min at 800 r/min; and then filtering, washing with deionized water, drying at 80 ℃ for 1.5 hours, adding 500g of lithium hydride powder with the particle size of 15 mu m and 500g of titanium hydride powder with the particle size of 17 mu m which are uniformly mixed as reducing agents, and grinding and mixing to obtain an intermediate product A.
Heating to 1000 ℃ at 10 ℃/min, preserving heat for 6 hours under argon atmosphere, and reducing the intermediate product A to obtain an intermediate product B. And (3) placing the intermediate product B into 5.0mol/L hydrochloric acid for pickling for 2 hours, washing with deionized water, filtering, and carrying out heat preservation at 80 ℃ for 2 hours to obtain the porous silicon/carbon composite material.
And (3) performing electrochemical performance test on the half battery formed by the porous silicon/carbon composite material and the metallic lithium, wherein the test multiplying power is 0.1C (first time) +0.5C (circulation), and the charge-discharge voltage is 0.005-2.0V. The specific discharge capacity of the negative electrode plate can reach 1920.8mAh/g, the first efficiency is 90.5%, and the capacity of the negative electrode plate can still be kept to 90.2% after 100 times of circulation.
Example 5:
50g of porous polyurethane microspheres with the particle size D50 of 18 mu m and the pore size of about 170nm are taken, added into a proper amount of water, heated to 55 ℃, stirred for 35min at 900r/min, and uniformly dispersed; then 3500g of ethyl silicate was slowly added to the resulting suspension and stirring was continued at 900r/min for 20min at 55 ℃; and filtering, washing with deionized water, drying at 90 ℃ for 1.5 hours, adding 700g of lithium hydride powder with the particle size of 15 mu m and 800g of titanium hydride powder with the particle size of 18 mu m which are uniformly mixed as reducing agents, and grinding and mixing to obtain an intermediate product A.
Heating to 1000 ℃ at 15 ℃/min, preserving heat for 8 hours under argon atmosphere, and reducing the intermediate product A to obtain an intermediate product B. And (3) placing the intermediate product B into 7.0mol/L hydrochloric acid for pickling for 3 hours, washing with deionized water, filtering, and carrying out heat preservation at 80 ℃ for 2 hours to dry to obtain the porous silicon/carbon composite material.
And (3) performing electrochemical performance test on the half battery formed by the porous silicon/carbon composite material and the metallic lithium, wherein the test multiplying power is 0.1C (first time) +0.5C (circulation), and the charge-discharge voltage is 0.005-2.0V. The specific discharge capacity of the negative electrode plate can reach 1830.6mAh/g, the first efficiency is 89.5%, and the capacity of 93.2% can be still maintained after 100 cycles.
Example 6:
50g of porous polystyrene microspheres with the particle size D50 of 25 mu m and the pore size of about 200nm are taken, added into a proper amount of water, heated to 60 ℃, stirred for 40min at 2000r/min, and uniformly dispersed; then 5000g of ethyl silicate was slowly added to the obtained suspension solution, and stirring was continued at 2000r/min at 60℃for 40min, and the mixed solution was sequentially filtered, washed with deionized water, dried at 100℃for 3 hours, and then 500g of lithium hydride powder having a particle size of 20 μm and 500g of aluminum powder having a particle size of 20 μm were added as reducing agents, and ground and mixed to obtain intermediate product A.
Heating to 1100 ℃ at 20 ℃/min, preserving heat for 8 hours under vacuum atmosphere, and reducing the intermediate product A to obtain an intermediate product B. And (3) placing the intermediate product B into 7.0mol/L hydrochloric acid for pickling for 3 hours, washing with deionized water, filtering, and carrying out heat preservation at 100 ℃ for 3 hours to obtain the porous silicon/carbon composite material.
And (3) performing electrochemical performance test on the half battery formed by the porous silicon/carbon composite material and the metallic lithium, wherein the test multiplying power is 0.1C (first time) +0.5C (circulation), and the charge-discharge voltage is 0.005-2.0V. The specific discharge capacity of the negative electrode plate can reach 1460.5mAh/g, the first efficiency is 88.3%, and the capacity of 89.6% can be maintained after 100 cycles.
Comparative example 1:
adding 1mol/L H of silicon powder with the grain size D50 of 0.5 mu m 2 SO 4 H with mass fraction of 2% 2 O 2 And 0.5mol/L HF, mechanically stirring for 1h at room temperature at 100r/min, removing impurities and surface silicon dioxide, cleaning with deionized water, and drying at 80 ℃ to obtain the nano silicon powder material.
The obtained nano silicon powder material and metallic lithium form a half cell to perform electrochemical performance test, wherein the test multiplying power is 0.1C (first time) +0.5C (circulation), and the charge and discharge voltage is 0.005-2.0V. The specific discharge capacity of the negative electrode plate can reach 2330mAh/g, the first efficiency is 72.3%, and the capacity retention rate is only 26.2% after 100 cycles.
Comparative example 2:
the silica powder having a particle size d50=3 μm was heat-treated in a reactor at 950 ℃ for 3 hours to obtain intermediate a.
Crushing, crushing and grading the intermediate product A, and then putting the intermediate product A into a rotary furnace to coat carbon for 3 hours at 800 ℃ in the atmosphere of mixed gas of acetylene, ethylene and argon, wherein the flow rates of the acetylene, ethylene and argon are all 0.1mol/L, so as to obtain the silicon oxide/carbon composite material.
And (3) performing electrochemical performance test on the semi-battery formed by the obtained silicon oxide/carbon composite material and metallic lithium, wherein the test multiplying power is 0.1C (first time) +0.5C (circulation), and the charge-discharge voltage is 0.005-2.0V. The specific discharge capacity of the negative electrode plate can reach 1430mAh/g, the first efficiency is 80.1%, and the capacity retention rate is only 56.2% after 100 times of circulation.
As can be seen from the performance results in comparative examples 1 to 6 and comparative examples 1 to 2, the in-situ composite carbon layer of the porous silicon/carbon composite material finally successfully prepared by the technical scheme effectively inhibits the volume change of the material in the lithium intercalation and deintercalation process, also improves the problem that the micro-nano material of the material is easy to agglomerate, and further, the in-situ composite carbon layer can better improve the electrochemical properties such as conductivity, cycle stability, charge-discharge efficiency, rate performance and the like of the silicon negative electrode. The unique micro-nano pore reserves a lithium intercalation expansion space for silicon, and reduces the absolute volume change of the composite material in the charge and discharge process. Therefore, the porous silicon/carbon composite material prepared by the method has high conductivity, long-cycle stability and excellent high-rate charge and discharge performance.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (10)
1. The method for in-situ synthesis of the porous silicon/carbon composite anode material by taking the porous polymer microspheres as templates is characterized by comprising the following steps of:
s1: adding the porous polymer microspheres into water, heating and stirring to uniformly disperse the porous polymer microspheres and obtain a suspension solution;
s2: adding a silicon source into the suspension solution obtained in the step S1, and continuously heating and stirring to obtain a mixed solution;
s3: filtering, washing with deionized water, drying, adding reducing agent, grinding and mixing to obtain an intermediate product A;
s4: treating the intermediate product A through a thermal reduction process to obtain an intermediate product B;
s5: the intermediate product B obtained in the step S4 is subjected to acid washing, filtering, deionized water washing and drying to obtain a final product porous silicon/carbon composite anode material, wherein the porous silicon/carbon composite anode material has a uniform and mutually communicated three-dimensional pore structure, the contact area of the porous silicon/carbon composite material and an electrolyte solution is increased, the permeation and wetting of the electrolyte solution are facilitated, the diffusion path of lithium ions is shortened, and the reaction active sites are increased;
in the S1, the average particle diameter D50 of the porous polymer microsphere is 500 nm-25 mu m, the pore distribution is uniform, and the pore size is 20-200 nm;
s2, the mass ratio of the porous polymer microspheres to the silicon source is 1:1-1:100;
in S4, the thermal reduction process is: and carrying out thermal reduction on the intermediate product A in a vacuum or inert protective gas atmosphere, wherein the temperature of the thermal reduction process is 800-1100 ℃.
2. The method for in-situ synthesis of a porous silicon/carbon composite anode material by using porous polymer microspheres as templates according to claim 1, wherein in S1, the porous polymer microspheres are one or a mixture of a plurality of porous polystyrene microspheres, porous polyethylene microspheres, porous polyvinyl chloride microspheres, porous polypropylene microspheres and porous polyurethane microspheres;
the heating temperature in S1 and S2 is 40-60 ℃, the stirring time is 20-40 min, and the stirring speed is 200-2000 r/min.
3. The method for in-situ synthesis of a porous silicon/carbon composite anode material by using porous polymer microspheres as a template according to claim 1, wherein in S2, the silicon source is one or a mixture of more of ethyl silicate, methyl silicate, sodium silicate, methoxy silane, ethoxy silane, propoxy silane and butoxy silane.
4. The method for in-situ synthesis of a porous silicon/carbon composite anode material by using porous polymer microspheres as templates according to claim 1, wherein in S3, the drying temperature is 50-100 ℃ and the time is 1-3 h.
5. The method for in-situ synthesis of a porous silicon/carbon composite anode material by using porous polymer microspheres as a template according to claim 1, wherein in S4, the reducing agent is one or more of titanium hydride powder, lithium hydride powder and aluminum powder;
the particle size of the reducing agent is 3-20 mu m, and the mass ratio of the reducing agent to the silicon source is 5:1-1:5.
6. The method for in-situ synthesis of the porous silicon/carbon composite anode material by using the porous polymer microspheres as templates, according to claim 1, wherein in S4, the temperature rising speed is 2-20 ℃, and the heat preservation time is 1-8 hours.
7. The method for in-situ synthesis of porous silicon/carbon composite anode material by using porous polymer microspheres as a template according to claim 1, wherein in S4, the thermal reduction process is performed by using any one of a vacuum furnace, a box furnace, a tube furnace, a pusher kiln, a roller kiln and a rotary kiln.
8. The method for in-situ synthesis of the porous silicon/carbon composite anode material by using the porous polymer microspheres as templates, which is characterized in that in S5, hydrochloric acid or sulfuric acid with the concentration of 2.0-7.0 mol/L is adopted as pickling solution in the pickling process, and the pickling time is 0.5-3 h;
s5, the drying process is as follows: and drying under the vacuum or inert gas condition, wherein the drying temperature is 50-100 ℃ and the drying time is 1-3 h.
9. The porous silicon/carbon composite anode material synthesized in situ by taking porous polymer microspheres as templates is characterized in that the porous silicon/carbon anode material is obtained by the preparation method of any one of claims 1-8.
10. A lithium ion battery comprising the porous silicon/carbon composite anode material of claim 9.
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Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102208634A (en) * | 2011-05-06 | 2011-10-05 | 北京科技大学 | Porous silicon/carbon composite material and preparation method thereof |
| JP2013199402A (en) * | 2012-03-23 | 2013-10-03 | Kyoto Univ | Method for producing silicon |
| CN103427073A (en) * | 2013-08-05 | 2013-12-04 | 同济大学 | Preparation method of mesoporous Si/C composite microsphere as lithium battery negative electrode material |
| CN103779544A (en) * | 2014-01-07 | 2014-05-07 | 浙江大学 | Preparation method of porous silicon/carbon composite material |
| CN104821395A (en) * | 2015-04-09 | 2015-08-05 | 中国科学院宁波材料技术与工程研究所 | Silicon/carbon nano microspheres powder preparation method and application thereof |
| CN106450192A (en) * | 2016-10-14 | 2017-02-22 | 浙江天能能源科技股份有限公司 | Silicon/carbon composite material for lithium ion battery and preparation method and application thereof |
| CN106920938A (en) * | 2017-03-30 | 2017-07-04 | 天津中科先进技术研究院有限公司 | Silicon-carbon composite material and preparation method thereof |
| CN108172797A (en) * | 2017-12-27 | 2018-06-15 | 肇庆市华师大光电产业研究院 | A kind of preparation method of lithium sulfur battery anode material |
| CN108341415A (en) * | 2018-02-27 | 2018-07-31 | 西北大学 | A kind of preparation method of macroporous silica core-shell particles |
| CN109004203A (en) * | 2018-08-02 | 2018-12-14 | 内蒙古三信实业有限公司 | A kind of silicon-carbon composite cathode material and preparation method thereof |
| CN109244401A (en) * | 2018-09-04 | 2019-01-18 | 南京工业大学 | A kind of porous nano Si-C composite material and preparation method thereof using magnesium reduction process preparation |
| CN109755482A (en) * | 2017-11-01 | 2019-05-14 | 同济大学 | Silicon/carbon composite and preparation method thereof |
| CN109830670A (en) * | 2019-03-04 | 2019-05-31 | 郑州大学 | A kind of hollow sandwich type SiO of lithium ion battery negative material2/C/MoS2Hybrid microspheres |
| CN110098385A (en) * | 2019-01-16 | 2019-08-06 | 上海普澜特夫精细化工有限公司 | A kind of silicon-hard carbon composite material and preparation method |
| CN110518195A (en) * | 2019-07-03 | 2019-11-29 | 浙江工业大学 | A kind of preparation method and application of nano-silicon/graphene composite material |
| CN111029558A (en) * | 2019-12-25 | 2020-04-17 | 广东凯金新能源科技股份有限公司 | Silicon-carbon composite negative electrode material with hollow core-shell structure and preparation method thereof |
| CN111509212A (en) * | 2020-04-30 | 2020-08-07 | 厦门高容纳米新材料科技有限公司 | Silicon-carbon composite negative electrode material, negative electrode plate, preparation method of negative electrode plate and lithium ion battery |
-
2020
- 2020-08-14 CN CN202010818048.9A patent/CN114079045B/en active Active
Patent Citations (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102208634A (en) * | 2011-05-06 | 2011-10-05 | 北京科技大学 | Porous silicon/carbon composite material and preparation method thereof |
| JP2013199402A (en) * | 2012-03-23 | 2013-10-03 | Kyoto Univ | Method for producing silicon |
| CN103427073A (en) * | 2013-08-05 | 2013-12-04 | 同济大学 | Preparation method of mesoporous Si/C composite microsphere as lithium battery negative electrode material |
| CN103779544A (en) * | 2014-01-07 | 2014-05-07 | 浙江大学 | Preparation method of porous silicon/carbon composite material |
| CN104821395A (en) * | 2015-04-09 | 2015-08-05 | 中国科学院宁波材料技术与工程研究所 | Silicon/carbon nano microspheres powder preparation method and application thereof |
| CN106450192A (en) * | 2016-10-14 | 2017-02-22 | 浙江天能能源科技股份有限公司 | Silicon/carbon composite material for lithium ion battery and preparation method and application thereof |
| CN106920938A (en) * | 2017-03-30 | 2017-07-04 | 天津中科先进技术研究院有限公司 | Silicon-carbon composite material and preparation method thereof |
| CN109755482A (en) * | 2017-11-01 | 2019-05-14 | 同济大学 | Silicon/carbon composite and preparation method thereof |
| CN108172797A (en) * | 2017-12-27 | 2018-06-15 | 肇庆市华师大光电产业研究院 | A kind of preparation method of lithium sulfur battery anode material |
| CN108341415A (en) * | 2018-02-27 | 2018-07-31 | 西北大学 | A kind of preparation method of macroporous silica core-shell particles |
| CN109004203A (en) * | 2018-08-02 | 2018-12-14 | 内蒙古三信实业有限公司 | A kind of silicon-carbon composite cathode material and preparation method thereof |
| CN109244401A (en) * | 2018-09-04 | 2019-01-18 | 南京工业大学 | A kind of porous nano Si-C composite material and preparation method thereof using magnesium reduction process preparation |
| CN110098385A (en) * | 2019-01-16 | 2019-08-06 | 上海普澜特夫精细化工有限公司 | A kind of silicon-hard carbon composite material and preparation method |
| CN109830670A (en) * | 2019-03-04 | 2019-05-31 | 郑州大学 | A kind of hollow sandwich type SiO of lithium ion battery negative material2/C/MoS2Hybrid microspheres |
| CN110518195A (en) * | 2019-07-03 | 2019-11-29 | 浙江工业大学 | A kind of preparation method and application of nano-silicon/graphene composite material |
| CN111029558A (en) * | 2019-12-25 | 2020-04-17 | 广东凯金新能源科技股份有限公司 | Silicon-carbon composite negative electrode material with hollow core-shell structure and preparation method thereof |
| CN111509212A (en) * | 2020-04-30 | 2020-08-07 | 厦门高容纳米新材料科技有限公司 | Silicon-carbon composite negative electrode material, negative electrode plate, preparation method of negative electrode plate and lithium ion battery |
Non-Patent Citations (4)
| Title |
|---|
| SiO2空心球的制备与表征;吉钰纯等;武汉工程大学学报;第32卷(第3期);第82-84和88页 * |
| SiO2空心球的制备与表面形貌调控;都奎山等;化工新型材料;第47卷(第6期);第164-167页 * |
| 二氧化硅隔热涂料的制备及性能表征;武国栋;中国优秀硕士学位论文全文数据库 工程科技I辑(第2期);第24-25页 * |
| 基于有序介孔/大孔二氧化硅材料的制备及其应用研究;郭聪;中国优秀硕士学位论文全文数据库 工程科技I辑(第2期);第23-25页 * |
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